Method of preparing an aluminium-containing iron oxide nucleus

ABSTRACT

The invention relates to a method of preparing an aluminum-containing iron oxide nucleus with an α-FeOOH crystal structure from FeCl 2 . This nucleus is a suitable starting material for the preparation of iron oxide yellow and for use as a yellow coloring pigment.

BACKGROUND OF THE INVENTION

[0001] The invention relates to a method of preparing an aluminium-containing iron oxide nucleus with an α-FeOOH crystal structure from FeCl₂. This nucleus is a suitable starting material for the preparation of iron oxide yellow and for use as a yellow coloring pigment.

[0002] Synthetic iron oxides are usually prepared by the Laux method, the Penniman method, the precipitation method, the neutralisation method or the roasting method (Ullmann's Encyclopedia of Industrial Chemistry, 5^(th) edition, 1992, Vol. A20, pages 297 et seq.). The iron oxides thus obtained are generally employed as pigments.

[0003] Basically two processes are known for preparing fine-particle α-FeOOH (needle width between 5 and 30 nm):

[0004] the acid process and

[0005] the alkaline process.

[0006] In the acid process an iron (II) component, an iron salt dissolved in water, is introduced initially and an alkaline component is added to it in metered quantities and with intensive mixing; the alkaline component is generally an alkali metal or alkaline earth metal compound dissolved or suspended in water or an ammonia solution. The quantity of alkaline component added is generally between 15% and 70% of the stoichiometrically required quantity. The pH after its addition is within the slightly acid range. When the addition of the alkaline component is over the material is oxidized with an oxidant, usually atmospheric oxygen. The reaction is carried out at temperatures between 20 and 50° C. At considerably higher temperatures there is a danger of undesirable magnetite forming. The end of the reaction can be recognized by a sharp drop in pH and redox potential. When the reaction is over the properties of the product obtained (generally described as the nucleus) are determined and the product—if suitable—is processed immediately to form an α-FeOOH pigment.

[0007] The alkaline process differs from the acid process in the quantity of alkaline component. In the alkaline process it is at least about 120% of the stoichiometrically required quantity and generally considerably more. The temperatures at which the reaction is carried out may be slightly above those used in the acid process as there is less danger here of magnetite forming.

[0008] The alkaline process basically produces relatively long-needled α-FeOOH crystallites with a length to width ratio of 10:1 to 30:1. As these crystallites also contain very few dendrites the process is particularly suitable for preparing α-FeOOH as a starting material for magnetic tapes.

[0009] Nuclei prepared by the alkaline process cannot be employed directly - or only to a limited extent—for making α-FeOOH pigments for use in paints and lacquers, as all the other coloring metals present in the industrially used Fe component become incorporated during the process. These metals (particularly Mn, Cr, Cu, Ni) have a considerably adverse effect on color properties, thereby restricting the use of nuclei thus prepared for the production of coloring pigments.

[0010] In the preparation of iron oxide pigments it is preferable to start with an α-FeOOH nucleus and then to coarsen it (build it up) in the acid substance, thereby diminishing the introduction of coloring metals. Furthermore the build-up must only take place at pH levels below about 4, as coloring metals are introduced to an increasing extent at higher pH levels. Moreover, the particle shape of the α-FeOOH considerably affects the color properties, the viscosity of the lacquer and the requirements for the binder.

[0011] Short-needle α-FeOOH particles are necessary in order to obtain the desired low viscosity in the lacquer and little binder requirements. These can be made by intensively grinding long-needle α-FeOOH particles. A more favourably priced alternative is direct preparation of short-needle α-FeOOH particles.

[0012] Modifying additives are required in order to guide the particle shape of the α-FeOOH nucleus and thus that of the pigment built up therefrom towards a low length to width ratio. The use of B, Al, Ga, Si, Ge, Sn or Pb as nucleus modifiers is known from U.S. Pat. No. 4 620 879. This patent specification describes an iron oxide yellow with a particularly low Silking index, achieved through an appropriate pigment build-up procedure and addition of the modifiers listed above. Although the specification describes the use of FeCl₂ it does not mention the exact conditions for preparing an α-FeOOH nucleus from FeCl₂. However since FeCl₂ clearly differs from FeSO₄, especially in the nucleus-forming phase, the conditions under which a good pigment is obtained with FeSO₄ cannot be transferred to FeCl₂.

[0013] An object of the invention was to provide a method of preparing a short-needle α-FeOOH nucleus by the precipitation process in a simple and cost-effective way. In a further step the α-FeOOH nucleus is built up to form an α-FeOOH pigment. The object is solved by the method of the invention.

SUMMARY OF THE INVENTION

[0014] The invention relates to a method of preparing aluminium-containing iron oxide nuclei with an α-FeOOH crystal structure with an aspect ratio (AR) of 2100 to 3600 and a BET surface area of 50 to 150 m2/g using FeCl₂, comprising the steps of

[0015] a) initially adding 4-13 mol %, based on the total iron, of an Al component to an iron (II) chloride solution with a total Fe content of 20-100 g/l, and an Fe (III) content of 0.1 to 10 mol % Fe (III) (based on the total Fe)

[0016] b) heating the mixture to a precipitation temperature between 30 and 60° C.,

[0017] c) adding a precipitating agent with an active ingredient content of 2-10 equivalents per liter, to the mixture and the molar ratio of Fe+Al to precipitating agent is 20-80% of the stoichiometric quantity,

[0018] d) oxidizing the precipitated suspension by an oxidant at a speed such that the oxidation rate is 2-50 mol %/h of the iron to be oxidized.

DETAILED DESCRIPTION OF THE INVENTION

[0019] In the context of the present invention the aspect ratio is the product of the BET surface area and the mean crystallite size, determined from the 110 reflex of the α-FeOOH by X-ray crystallography.

[0020] The Al-containing α-FeOOH nucleus obtained after oxidation may optionally by used to prepare iron oxide yellow pigments without further separation, when its properties have been tested.

[0021] The process preferably uses

[0022] a) an iron (II) chloride solution with a total Fe content of preferably 40-65 g/l,

[0023] b) a precipitation temperature between 35 and 50° C.,

[0024] c) a precipitating agent with an active ingredient content of 4-8 equivalents per liter, c) a molar ratio of Fe+Al to precipitating agent of 30-60% of the stoichiometric quantity, and

[0025] The Al-containing α-FeOOH nucleus obtained after oxidation is separated if appropriate.

[0026] It is more preferred to proceed as follows:

[0027] Initial Chemicals:

[0028] FeCl₂ solution with an Fe content of 55 g/l Fe, including 1.5 mol % Fe (III)

[0029] AlCl₃ solution

[0030] NaOH solution with an NaOH content of 300 g/l=7.5 equivalents NaOH/l

[0031] Al/Fe ratio: 12-13

[0032] Proportion of Fe+Al/precipitating agent: 35-40%

[0033] Reaction Conditions:

[0034] Temperature: 44° C.

[0035] Oxidation speed: 30-35 mol % Fe (II)/h

[0036] AlCl₃ (as an aqueous solution) is preferably employed as the Al component. The use of Si or Ti as nucleus modifiers, in their chloride form, is also possible but entails a greater industrial outlay on production.

[0037] NaOH, KOH, Na₂CO₃, K₂CO₃, Mg(OH)₂, MgO, MgCO₃, Ca(OH)₂, CaO, CaCO₃, NH₃ or secondary or tertiary aliphatic amines may be used as precipitating agents in an aqueous solution or an aqueous slurry.

[0038] The oxidant used may be atmospheric oxygen, oxygen, ozone, H₂O₂, chlorine, nitrates of alkali metals or alkaline earth metals or NH₄NO₃.

[0039] If the iron (II) chloride solution employed contains quite large quantities of precipitable coloring metals at pH levels below 4, these may be precipitated by adding an alkaline component to the iron (II) chloride solution up to pH 4. The solid formed may be separated from the remaining clear, purified solution by sedimentation, filtering or centrifuging. Not only are the undesirable coloring metals removed but also Fe (III), which has a seriously undesirable effect on the reaction to form the α-FeOOH nucleus (it forms black magnetite).

[0040] The reaction takes place in discontinuous or continuous agitating boilers, in cascades of agitating boilers, loop-type reactors or reactors without agitators and with dual-material nozzles as mixing members.

[0041] When the α-FeOOH nuclei according to the invention have been prepared they are converted to a pigment by the known process of coarsening the nucleus particles (building up the pigment). But as the α-FeOOH nuclei according to the invention are not used as such it is necessary to describe how the pigment is built up to form an iron oxide yellow pigment.

[0042] The Al-containing nucleus prepared by the method of the invention is pumped to a solution of FeCl₂ or FeSO₄ or a different Fe (II) salt. 7-15 mol Fe (II) salt, as a solution with an Fe content of 30-100 g/l Fe, is used per mol of FeOOH in the nucleus. Addition of larger quantities of Fe (II) salt does also produce α-FeOOH yellow pigments but the brightness diminishes as the quantity of added Fe (II) salts is increased, which is generally undesirable. The suspension is heated to the reaction temperature, which is between 50 and 90° C. When the precipitation temperature has been reached oxidation and precipitation are started simultaneously. Atmospheric oxygen is generally added through a suitable gas supplying device and the pH of the suspension is adjusted with an alkaline precipitating agent. The pH is adjusted within the 2.4 to 4.8 range. The oxidation speed should be between 0.5 and 8 mol % Fe (III)/h.

[0043] When the reaction is over (i.e. when all the Fe (II) has been oxidized) the solid formed is filtered off. It is washed to remove the salt and can then be dried.

[0044] The yellow pigment made by this method is distinctive in its very pure color, almost isometric particle shape, low oil absorption number and high chemical purity. The sum of its properties makes it particularly suitable for:

[0045] application in the field of paints and lacquers

[0046] applications as a raw material for catalysts

[0047] applications in the food coloring field

[0048] applications in the paper coloring field

[0049] applications in the polymer coloring field

[0050] applications as a UV stabiliser

[0051] applications in the field of high-grade building materials (plasters etc)

[0052] applications in the field of dispersion colors

[0053] Due to the cost-effective raw materials and the high production rate in preparing the yellow pigment the process is particularly economical. Due to the special reaction process and use of a precisely specified nucleus one can prepare especially high-grade yellow pigments which are more advantageous to use than pigments made by other methods.

[0054] Environmentally relevant chemicals are not employed in preparing the yellow pigments according to the invention.

[0055] In the preferred embodiment (with FeCl₂, AlCl₃, NaOH and air used as the ingredients) an almost closed circuit is possible through electrolysis of the NaCl obtained as a by-product. The resultant sodium hydroxide solution may be re-used directly in the process. The H₂ and Cl₂ produced by the chlor-alkali electrolysis can be converted to HCl, which can in turn be used for etching the steel plates. This particularly environmentally friendly technology is not at present possible with FeSO₄ as electrolysis of FeSO₄ does not work satisfactorily.

[0056] Description of the Measuring Methods Used

[0057] 1. Measuring the BET Surface Area

[0058] The BET surface area is determined by the so-called one point method to DIN 66131. 90% He and 10% N₂ are used as the gas mixture and the measurement is taken at 77.4 K. The sample is heated for 60 minutes at 140° C. before measuring.

[0059] 2. Radiographic Measurement of the Crystallite Size

[0060] The crystallite size is determined on the Phillips powder diffractometer. The 110 reflex is used for this purpose.

[0061] α-iron oxide hydroxide (M(FeOOH)=88.9 g/mol

[0062] 2.1 Field of Application

[0063] Determining crystallite size in goethite within the 5 to 100 nm range.

[0064] 2.2 Basic Method

[0065] The size in goethite is determined after X-ray diffractometric radiation through reflection detection. The evaluation is made using silicon as an external standard.

[0066] 2.3 The Reagent

[0067] Silicon standard for angular calibration (ICDD no. 27-1402), Philips PW 1062/20

[0068] TABLE 1 Peak parameters of silicon reflex Parameters Position, top value, (° 2theta) 28.45746 Net height (counts) 8588.32 Background height at peak position (counts) 66.56 Net area (° 2theta * counts) 1182 Background area (° 2theta * counts) 200 FWHM (° 2theta) 0.0976 Integral breadth (° 2theta) 0.1376 FWHM/integral breadth 0.7094 Asymmetry 0.99 Background Low angle side (° 2theta) 27.02000 (counts) 61.58 High angle side (° 2theta) 29.98000 (counts) 71.75

[0069] TABLE 2 Peak parameters of goethite sample: Crystallite size 46.5 nm Position, top value, (° 2theta) 21.25219 Net height (counts) 2120.73 Background height at peak position (counts) 44.92 Net area (° 2theta * counts) 589 Background area (° 2theta * counts) 237 FWHM (° 2theta) 0.2061 Integral breadth (° 2theta) 0.2779 FWHM/integral breadth 0.7415 Asymmetry 1.16 Background Low angle side (° 2theta) 18.54000 (counts) 58.38 High angle side (° 2theta) 23.67000 (counts) 33.05

[0070] TABLE 3 Crystallite size determination with X'Pert program: Scherrer equation Menu option: Additional functions in X'Pert program section: X'Pert organiser Anode material Cu (copper) Radiation type Cu Kα Wavelength (nm) 0.154184 K factor (mean shape factor) 0.9000 CuKα₁/CuKα₂ intensity ratio 0.5000 Signal width of Lattice Crystal- broaden- Signal Particle size tension Signal lite ing breadth broadening broadening position size (°2theta) (°2theta) (°2theta) (°2theta) (°2theta) (nm) 0.1376 0.0976 0.0400 0.0970 28.45500 205.1 0.2779 0.0976 0.1803 0.2602 21.25400 44.9 0.2766 0.0976 0.1790 0.2588 21.25100 45.2 0.8814 0.0976 0.7838 0.8760 21.22800 10.3 0.9325 0.0976 0.8349 0.9274 21.24400 9.7 0.4287 0.0976 0.3311 0.4174 21.22090 24.4 0.4274 0.0976 0.3298 0.4161 21.21911 24.5

[0071] 4. Measurement of Color Values

[0072] Color values are measured as described in EP-A 0 911 370.

EXAMPLES Example 1 Aluminium-Containing Nucleus of FeCl₂ and AlCl₃

[0073] 14.095 liters of FeCl₂ solution with 55.07 g/l Fe and an Fe (III) content of 1.5 mol % (relative to total Fe) was placed in a discontinuous agitating boiler with a useful volume of 30 liter, equipped with a three-stage cross-arm agitator and a gas supply device (a ring with holes below the agitator). 914g of AlCl₃ solution with 5.06% by weight of Al and 3.95% of HCl was then added.

[0074] The quantity of FeCl₂ corresponded to 13.9 mol Fe (Fe (II) and Fe (III)), the quantity of AlCl₃ to 1.71 mol and that of HCl to 0.989 mol. The Al/total Fe ratio accordingly corresponded to 12.3 mol % relative to total Fe. This solution was heated to 44° C. with agitation and with nitrogen supplied at 300 Nl/h. When this temperature had been reached 1615 ml of soda lye containing 300 g NaOH/l (corresponding to 7.5 equivalents per liter) was pumped in with a gear pump in 6 minutes. 33.8% of the metals Fe+Al were therefore precipitated. As soon as the precipitation was over the supply of nitrogen was stopped and 97 Nl/h of air was supplied for oxidation. The reaction was terminated 180 minutes after the beginning of oxidation. The oxidation speed was accordingly 33.3 mol % Fe (II)/h. (This took into account only the 33.8% of the Fe which was precipitated by the NaOH. The Fe (III) part was counted as Fe (II). It was also assumed that Fe and Al were precipitated equally).

[0075] The nucleus obtained had the following properties: BET surface area: 100 m²/g Crystallite size: 27.0 nm AR: 2700

Comparative Example 1 Aluminium-Containing Nucleus of FeCl₂ and AlCl₃

[0076] 14.095 liters of FeCl₂ solution with 55.07 g/l Fe and an Fe (III) content of 1.5 mol % (relative to total Fe) is placed in a discontinuous agitating boiler with a useful volume of 30 liter, equipped with a three-stage cross-arm agitator and a gas supply device (a ring with holes below the agitator). 914g of AlCl₃ solution with 5.06% by weight of Al and 3.95% of HCl is then added.

[0077] The quantity of FeCl₂ corresponds to 13.9 mol Fe (Fe (II) and Fe (III)), the quantity of AlCl₃ to 1.71 mol and that of HCl to 0.989 mol. The Al/total Fe ratio accordingly corresponds to 12.3 mol % relative to total Fe. This solution is heated to 34° C. with agitation and with nitrogen supplied at 300 Nl/h. When this temperature has been reached 1615 ml of soda lye containing 300 g NaOH/I (corresponding to 7.5 equivalents per liter) is pumped in with a gear pump in 6 minutes. 33.8% of the metals Fe+Al are therefore precipitated by the NaOH. As soon as the precipitation is over the supply of nitrogen is stopped and air is supplied at 97 Nl/h. The reaction is terminated 180 minutes after the beginning of oxidation. The oxidation speed is accordingly 33.3 mol % Fe (II)/h. (This takes into account only the 33.8% of the Fe which was precipitated by the NaOH. The Fe (III) part is counted as Fe (II). It is also assumed that Fe and Al were precipitated equally).

[0078] The nucleus had the following properties: BET surface area: 173 m²/g Crystallite size: 17.5 nm AR: 3027

[0079] Comparative Example 2

Aluminium-Containing Nucleus of FeCl₂ and AlCl₃

[0080] 11.58 liters of FeCl₂ solution with 55.09 g/l Fe and an Fe (III) content of 1.0 mol % (relative to total Fe) is placed in a discontinuous agitating boiler with a useful volume of 30 liter, equipped with a three-stage cross-arm agitator and a gas supply device (a ring with holes below the agitator). 818 g of AlCl₃ solution with 6.00% by weight of Al and 1.6% of HCl is then added.

[0081] The quantity of FeCl₂ corresponds to 9.5 mol Fe (Fe (II) and Fe (III)), the quantity of AlCl₃ to 1.82 mol and that of HCl to 0.36 mol. The Al/total Fe ratio accordingly corresponds to 19.2 mol % relative to total Fe. This solution is heated to 44° C. with agitation and with nitrogen supplied at 300 Nl/h. When this temperature has been reached 1061 ml of soda lye containing 300 g NaOH/l (corresponding to 7.5 equivalents per liter) is pumped in with a gear pump in 10 minutes. 32.1% of the metals Fe+Al are therefore precipitated by the NaOH. As soon as the precipitation is over the supply of nitrogen is stopped and air is supplied at 67 Nl/h. The reaction is terminated 135 minutes after the beginning of oxidation. The oxidation speed is accordingly 44.5 mol % Fe (II)/h. (This takes into account only the 32.1% of the Fe which was precipitated by the NaOH. The Fe (III) part is counted as Fe (II). It is also assumed that Fe and Al were precipitated equally).

[0082] The nucleus had the following properties: BET surface area: 186 m²/g Crystallite size: 15.5 nm AR: 2883

Example 4 Preparation of yellow pigment

[0083] 2 mol of yellow nucleus suspension from Example 1 (counted as mols of α-FeOOH) and 20 mol FeCl₂ with an Fe content of 95.7 g/l Fe are placed in a discontinuous agitating boiler with a gas supply ring, a pH meter, temperature control and a three-stage cross-arm agitator. The suspension is heated to 60° C. with constant agitation. When that temperature is reached a pH level of 3.4 is maintained by constant metered addition of soda lye. 76 Nl/h of air is fed in simultaneously. When the air has been fed in for 1618 minutes all the Fe (II) is oxidized, representing an oxidation speed of 3.7 mol % Fe/h.

[0084] The yellow pigment produced has the following properties: BET surface area: 32.7 m²/g Crystallite size: 27 nm Color intensity (against Bayferrox ®915): 97% da*: 0.2 db*: −1.2 dL* (against Bayferrox 915): −0.7 da*: 0.7 db*: −1.2

Example 5 Preparation of Yellow Pigment

[0085] If the nucleus from Example 2 is used instead of the nucleus from Example 1 and the quantity of air is set to 76 Nl/h, with the reaction conditions otherwise identical, a yellow pigment with the following properties is obtained after 1618 minutes (oxidation speed 3.7 mol %/h): BET surface area: 45.6 m²/g Crystallite size: 25 nm Color intensity (against Bayferrox 915): 97% da*: 0.1 db*: −2.6 dL* (against Bayferrox 915): −3.4 da*: 1.1 db*: −4.0

Example 6 Preparation of Yellow Pigment

[0086] If the nucleus from Example 3 is used instead of that from Example 1 the following yellow pigment is obtained under the reaction conditions of Example 5: BET surface area: 32.7 m²/g Crystallite size: 32 nm Color intensity (against Bayferrox 915): 101% da*: −0.9 db*: −2.1 dL* (against Bayferrox 915): −2.4 da*: −1.0 db*: −4.0

[0087] Only the pigment prepared with a nucleus according to the invention is similar enough in color to the comparative type Bayferrox 915 to be utilisable as a high-grade yellow pigment. The two yellow pigments prepared from the nuclei in the comparative examples are considerably too dark (the pure shade) and not yellow enough. 

What is claimed is:
 1. A method of preparing aluminium-containing iron oxide nuclei with an α-FeOOH crystal structure with an aspect ratio (AR) of 2100 to 3600 and a BET surface area of 50 to 150 m2/g using FeCl₂, comprising the steps of a) initially adding 4-13 mol %, based on the total iron, of an Al component to an iron (II) chloride solution with a total Fe content of 20-100 g/l, and an Fe (III) content of 0.1 to 10 mol % Fe (III) (based on the total Fe) b) heating the mixture to a precipitation temperature between 30 and 60° C., c) adding a precipitating agent with an active ingredient content of 2-10 equivalents per liter, to the mixture and the molar ratio of Fe+Al to precipitating agent is 20-80% of the stoichiometric quantity, d) oxidizing the precipitated suspension by an oxidant at a speed such that the oxidation rate is 2-50 mol %/h of the iron to be oxidized.
 2. The method of claim 1, wherein a) the total Fe content is 40-65 g/l.
 3. The method of claim 1, wherein b) the precipitation temperature is between 35 and 50° C.
 4. The method of claim 1, wherein c) the precipitating agent has an active ingredient content of 4-8 equivalents per liter.
 5. The method of claim 1, wherein c) the molar ratio of Fe+Al to precipitating agent is 30-60% of the stoichiometric quantity.
 6. The method of claim 1, wherein d) the oxidation rate is 10-35 mol %/h of the iron to be oxidized.
 7. The method of claim 1, wherein the Al component is aluminium chloride.
 8. The method of claim 1, wherein the precipitating agent is an aqueous solution or an aqueous slurry of NaOH, KOH, Na₂CO₃, K₂CO₃, Mg(OH)₂, MgO, MgCO₃, Ca(OH)₂, CaO, CaCO₃, NH₃, a secondary amine, or a tertiary aliphatic amine.
 9. The method of claim 1, wherein the oxidant is atmospheric oxygen, oxygen, ozone, H₂O₂, chlorine, a nitrate of the alkali metals or alkaline earth metals, or NH₄NO₃.
 10. The method of claim 1, wherein the reaction takes place in discontinuous or continuous agitating boilers, in cascades of agitating boilers, loop-type reactors or reactors without agitators and with dual-material nozzles as mixing members.
 11. A method of preparing a yellow pigment using the α-FeOOH nuclei prepared according to the process of claim
 1. 